New crystals in the lithium sulfate family

The preparation and structures of caesium lithium sulfate, Cs_1.15Li_2.85(SO₄)₂, and caesium lithium rubidium sulfate, Cs_0.90Li_2.88Rb_0.22(SO₄)₂, are described and discussed in the context of simple and double sulfate polymorphism. The latter structure is related to the former through the substitution of Rb for Cs. In both crystals, the sulfate ions occupy two non-equivalent sites, but the ions are disordered in Cs_1.15Li_2.85(SO₄)₂.

S1. Comment

Double sulfate crystals, (LiASO₄, with A = Na, K, Rb, Cs and NH₄), have been widely studied due to the rich variety of properties and phase transitions exhibited by these families. Among the compounds with this chemical formula, crystals can be found displaying ferroelectricity (Shiroishi et al., 1976), ferroelasticity (Pakulski et al., 1983), superionic conduction (Karlsson & McGreevy, 1995) and incommensurate phases (Mashiyama et al., 1979). In general, double sulfates crystallize in a tridymite-like structure where A cations are piled along the c axis at the vertices of pseudo-hexagonal networks, which are distributed inside layers of SO₄ tetrahedra. Li cations are located at vacancies of the network between the layers (Aleksandrov, 1993).

Two polymorphic families are observed in double sulfate compounds due to distortions of the pseudo-hexagonal lattice. The first corresponds to lattices with hexagonal basis vectors or closely related structures, such as, for example, a monoclinic lattice with a_h ≈ b_h and β ≈ 120°. Another form of polymorphism is characterized by a set of orthogonal axes, which are related to the hexagonal axes by a_o = a_h, b_o = a_h and c_o = c_h, or slight distortions of ??it??, such as a monoclinic lattice with one of the internal angles close to 90°. It is known that the different forms of polymorphism are closely related to the dynamics and possible orientations of the tetrahedral SO₄ groups in the structure and the ionic radius of the A cation. As an example of these polymorphs, we show in Fig. 1 the crystal structures of Cs₂SO₄ and KLiSO₄, where the distorted and regular hexagonal lattices can be observed. The A cation lattice dependence is particularly evident in mixed crystals [Li(A'A")SO₄], in which the crystal structure and the phase transition sequence are strongly dependent on the concentration and radius of the alkaline cations.

Usually, simple and mixed double sulfates grow from aqueous solutions containing stoichiometric mixtures of the simple sulfate salts Li₂SO₄·H₂O, A'₂SO₂ and, if necessary, A"₂SO₄. Generally, alkaline sulfate salts give rise to structures with mainly the same characteristics as double sulfates. However, Li₂SO₄ and Li₂SO₄·H₂O crystallize in a different structure pattern because the small lithium radius is not able to support the pseudo-hexagonal network, and consequently Li cations are approximately aligned to the basal plane of the SO₄ tetrahedra.

Recently, on the basis of X-ray powder diffraction and Raman scattering, a new phase in the LiRbSO₄-LiCsSO₄ system was characterized (Lima et al., 2000). This phase seems to be stable over variations of the growing conditions. Polarized Raman spectra and X-ray powder diffraction suggest that the crystal structure is monoclinic, with point group C_s. Moreover, the lattice parameters are a = 15.983 (6), b = 5.050 (4), c =5.191 (7) Å and β = 90.22°, which cannot be interpreted as a simple distortion of the tridymite network.

Based on these results, several attempts to grow high-quality single crystals with the structure reported by Lima et al. (2000) were carried out, in order to obtain samples suitable for structure determination. We report here single-crystal X-ray diffraction studies of two crystals obtained from different salt mixtures, with formulae Cs_1.15Li_2.85(SO₄)₂ (I) and Cs_0.90Li_2.88Rb_0.22(SO₄)₂ (II), established from the least-squares refinement, which have structures closely related to those reported by Lima et al. (2000). These structures do not exhibit the same features as most other alkali sulfates, where pseudo-hexagonal networks composed of SO₄ and one kind of cation are piled along the c axis (typical of the tridymite-like structures) and the other kind of cation is located at vacancies in the network between the layers (Aleksandrov, 1993).

Compound (I) is orthorhombic, and projections of the structure on the ac and bc planes are shown in Figs. 2a and 2 b. The Cs ions occupy two different Wyckoff positions, a and b. Several refinement tests indicated that atoms in position a have full occupancy, while atoms in position b have partial occupancy [0.15 (2)]. Li ions were refined with their site occupancies constrained such that, together with the Cs ions, the total charge is two. The structure was found to be a racemic twin, the fractional component of the inverted structure being 0.53 (6) (Flack, 1983). Besides the Li and Cs occupational disorder observed in the structure, the O atoms located at the basal plane of the SO₄ group are also disordered, thus allowing two possible orientations for this group. As shown in Fig. 2c, O₁₁ atoms are located at the apex site of the tetrahedra centered in S₁, while the two possible bases are determined by each set of O₂₁, O₁₂ and O₁₄ atoms. The coordination of the S₂ atom is also shown in Fig. 2c and is similar to that around S₁.

Compound (II) is monoclinic, and projections of the structure on the ac and bc planes are shown in Figs. 3a and 3 b. The Cs and Rb ions occupy two different general positions, both with partial occupancies. Several refinement tests ruled out the possibility that these sites are shared by both ions. Li ions were refined, as in the previous structure, with their site occupation factors constrained such that, together with the Cs and Rb ions, the total charge is two. No disorder of the SO₄ groups was observed in this crystal. Furthermore, the structure is consistent with the previous Raman scattering study, which indicated a monoclinic lattice with C_s symmetry (Lima et al., 2000).

Despite the fact that both refinements were carried out independently with different space groups and chemical formulae, the structures are nearly isomorphous. In fact, each structure can be refined with the diffraction data of the other, although, of course, ?the refinement converges? to higher R1 factors. Via a comparison of both crystal structures (Fig. 2 and 3) it is possible to identify the main similarities and differences between them. Notice that the unit cell of (I) has been shifted by (0,0,1/4) in order to help the comparison. In (II) the monoclinic angle β= 90.297 (2)° may be thought of as a distortion from the orthorhombic 90° angle, which results in the removal of the mirror plane. Cation substitution influences the ordering of the SO₄ groups in the crystal structure. In the orthorhombic structure, (I), the SO₄ groups are found with two equally probable orientations, while in the monoclinic structure, (II), the SO₄ groups are well ordered. Although orientational disorder of the SO₄ groups is only observed in (I), the main orientation of these groups is the same as that in (II). Li₂ and Li₁ do not change their positions relative to the SO₄ groups, while in (II), Li₃ is almost aligned with Li₁, thus forming a plane perpendicular to the [001] direction. The main difference between the two structures can be observed in the Li₄ and heavy-cation distribution. In (I), the Cs cations are aligned in the [100] direction, alternating full and partially occupied sites, and the Li₄ cations are intercalated among one of the SO₄ layers, while in (II) the Rb ions are shifted from the line determined by the Cs cations and partially occupy the Li₄ site, ??as Li₄ is?? not present in this structure.

Finally, we would like to comment on the reported structures in the context of simple and double sulfate polymorphism. It has been pointed out that double sulfates are characterized by a pseudo-hexagonal network determined by the heavy ions, within which layers of SO₄ groups perpendicular to the pseudo-hexagonal axis are distributed. A comparison of structures representative of simple and double sulfate polymorphism (Fig. 1) with the projection of (I) (Fig. 2 b) and (II) (Fig. 3 b) on the bc plane reveals an atomic pattern similar to that observed in the pseudo-hexagonal network; this pattern is represented by dashed lines in the figures. On the basis of this lattice, we can associate the a_h and c_h hexagonal axis with the a_o(a_m) and b_o(b_m) axis of the orthorhombic (monoclinic) cell, respectively. Note that the a_b pseudo-axis value corresponds approximately to that measured in double sulfates, but the c_h pseudo-axis is much shorter. This contraction is due to the low occupation of the heavy-ion sites, which are responsible for the pseudo-hexagonal framework. Furthermore, in the structures reported in this work, the SO₄ groups are not intercalated between the planes determined by the heavy ions but lie in the same planes (see Figs. 2a and 3a). The c_h-axis contraction does not allow Li ions to be placed on the top of the SO₄ tetrahedra (see Fig. 1 b), but the Li ions occupy interstitial sites between these groups. According to the previous discussion, the c axis of the monoclinic and orthorhombic lattices reported in this work should be associated with the b_o axis of the orthorhombic polymorphism of sulfate crystals, which is expected to be a multiple of (3)^1/2a_h. Thus, in spite of the small contraction, it is observed that c≈2(3)^1/2a. These results complete the correspondence bewteen the crystal structures of (I) and (II) with the usual polymorphism of the simple and double sulfate crystals.

S2. Experimental

Small single crystals of (I) and (II) were grown by the vapor-diffusion technique (Henisch, 1996) at controlled temperature (293 K) and pH (9). Two saturated solutions containing molar ratios of 2:1:1 of Li₂SO₄, Cs₂SO₄ and Rb₂SO₄ and 1:0.1 of Li₂SO₄ and Cs₂SO₄ were prepared in distilled and de-ionized water, thus producing small crystals of (I) and (II), respectively.

S3. Refinement

Colorless prismatic single crystals of both compounds were selected with the aid of a polarizing microscope. The occupancies of the cations were refined initially and then fixed for the final refinement. Occupancies for (I) were found to be Cs2 0.15 (2), Li2 0.32 (3), Li3 0.20 (2) and Li4 0.40 (3). Occupancies for (II) were found to be Cs 0.90 (1), Rb 0.22 (1), Li1 0.94 (2) and Li2 0.94 (2).

Computing details

Data collection: Collect (Enraf–Nonius, 1997-2000) for (I); Collect (Nonius BV, 1997-2000) for (II). Cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997) for (I); HKL SCALEPACK (Otwinowski & Minor 1997) for (II). Data reduction: HKL DENZO and SCALEPACK (Otwinowski & Minor, 1997) for (I); HKL DENZO and SCALEPACK (Otwinowski & Minor 1997) for (II). For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999).

Figures

	Fig. 1. Projection of the crystals structures of (a) Cs2SO4 along the a axis and (b) KLiSO4 along the c axis. Cs and Li atoms are represented by large and small spheres, respectively. Dashed lines show the pseudo-hexagonal network.
	Fig. 2. Projections of the crystal structure of Cs1.15Li2.85(SO4)2 along the (a) b and (b) a axis. Large, medium and small spheres represent Cs2, Cs1 and Li cations, respectively. The small spheres become darker indicating different Li positions (from 1 to 4). The dashed lines show the pseudo-hexagonal network. The atomic coordination of the (c) S1 and (d) S2 is also shown.
	Fig. 3. Projection of the crystal structure of Cs0.90Li2.88Rb0.22(SO4)2 along the (a) b and (b) a axis. Large, medium and small spheres represent Rb, Cs and Li cations, respectively. The small spheres become darker indicating different Li positions (from 1 to 3). The dashed lines show the pseudo-hexagonal network.

(I) caesium lithium sulfate

Crystal data

Cs1.15Li2.85(SO4)2	F(000) = 337
Mr = 364.77	Dx = 2.872 Mg m^−3
Orthorhombic, Pmc21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2	Cell parameters from 17795 reflections
a = 5.0620 (2) Å	θ = 1.0–27.5°
b = 5.2230 (3) Å	µ = 5.55 mm^−1
c = 16.0060 (9) Å	T = 293 K
V = 423.18 (4) Å^3	Prism, colorless
Z = 2	0.29 × 0.19 × 0.08 mm

Data collection

KappaCCD diffractometer	1065 independent reflections
Radiation source: fine-focus sealed tube	1053 reflections with I > 2σ(I)
Horizonally mounted graphite crystal monochromator	Rint = 0.032
Detector resolution: 9 pixels mm^-1	θmax = 27.5°, θmin = 2.5°
ϕ scans and ω scans with κ offsets	h = −6→6
Absorption correction: multi-scan multi-scan from symmetry-related measurements SORTAV (Blessing, 1995)	k = −6→6
Tmin = 0.290, Tmax = 0.661	l = −20→20
1740 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0969P)^2 + 0.7843P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.044	(Δ/σ)max = 0.006
wR(F^2) = 0.133	Δρmax = 0.96 e Å^−3
S = 1.07	Δρmin = −0.87 e Å^−3
1064 reflections	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
109 parameters	Extinction coefficient: 0.166 (17)
1 restraint	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.50 (6)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cs1	0.0000	0.73578 (12)	0.73304 (8)	0.0435 (4)
Cs2	−0.5000	0.7927 (15)	0.8695 (9)	0.076 (2)	0.15
S1	0.0000	0.3338 (5)	0.9399 (3)	0.0342 (6)
S2	0.5000	0.2659 (4)	0.6459 (2)	0.0323 (7)
O11	0.0000	0.6152 (18)	0.9503 (6)	0.052 (2)
O12	−0.105 (4)	0.2508 (16)	0.8594 (11)	0.044 (3)	0.50
O13	−0.292 (3)	0.2743 (19)	0.9397 (11)	0.045 (3)	0.50
O14	−0.122 (2)	0.806 (2)	0.5115 (9)	0.041 (3)	0.50
O21	0.5000	0.5347 (16)	0.6273 (6)	0.063 (3)
O22	−0.412 (3)	1.222 (2)	0.7254 (14)	0.046 (3)	0.50
O23	−0.3666 (18)	1.1020 (19)	0.5844 (9)	0.048 (2)	0.50
O24	−0.206 (4)	1.2204 (19)	0.6371 (13)	0.045 (3)	0.50
Li1	0.0000	0.146 (3)	0.5411 (12)	0.036 (3)
Li2	−0.5000	1.168 (6)	0.8464 (14)	0.025 (4)	0.65
Li3	−0.5000	0.889 (9)	0.631 (2)	0.025 (4)	0.40
Li4	−0.5000	0.786 (4)	0.924 (2)	0.036 (3)	0.80

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cs1	0.0462 (5)	0.0380 (5)	0.0463 (5)	0.000	0.000	0.0003 (4)
Cs2	0.078 (6)	0.058 (4)	0.092 (8)	0.000	0.000	0.001 (4)
S1	0.0343 (11)	0.0330 (13)	0.0355 (11)	0.000	0.000	0.0007 (10)
S2	0.0358 (15)	0.0280 (13)	0.0332 (15)	0.000	0.000	−0.0006 (9)
O11	0.065 (5)	0.051 (5)	0.041 (4)	0.000	0.000	0.001 (4)
O12	0.049 (8)	0.049 (8)	0.035 (6)	−0.019 (4)	−0.022 (6)	0.006 (4)
O13	0.030 (6)	0.047 (6)	0.057 (8)	−0.004 (4)	0.007 (6)	0.001 (5)
O14	0.028 (5)	0.028 (4)	0.068 (7)	−0.002 (4)	−0.013 (5)	−0.012 (5)
O21	0.112 (8)	0.034 (4)	0.043 (4)	0.000	0.000	0.016 (4)
O22	0.055 (6)	0.063 (6)	0.022 (7)	−0.006 (4)	−0.001 (6)	0.001 (5)
O23	0.045 (5)	0.045 (5)	0.053 (5)	0.006 (4)	0.027 (6)	−0.004 (6)
O24	0.032 (7)	0.035 (5)	0.067 (9)	0.006 (5)	−0.012 (6)	−0.008 (5)
Li1	0.041 (7)	0.021 (6)	0.046 (8)	0.000	0.000	0.004 (5)
Li2	0.031 (9)	0.025 (12)	0.018 (9)	0.000	0.000	−0.009 (7)
Li3	0.031 (9)	0.025 (12)	0.018 (9)	0.000	0.000	−0.009 (7)
Li4	0.041 (7)	0.021 (6)	0.046 (8)	0.000	0.000	0.004 (5)

Geometric parameters (Å, º)

Cs1—O24	3.138 (14)	S1—O11	1.479 (10)
Cs1—Li3	3.12 (2)	S1—O13	1.509 (15)
Cs1—O21	3.221 (6)	S2—O21	1.435 (8)
Cs1—O22	3.285 (15)	O12—O13	1.60 (2)
Cs1—O12	3.285 (13)	O22—O24	1.76 (3)
Cs2—Li4	0.87 (3)	O22—Li2	2.01 (3)
Cs2—Li2	1.99 (3)	O22—Li3	2.35 (4)
Cs2—O11	2.990 (8)	O23—O24	1.33 (2)
Cs2—O13	3.116 (15)	O23—Li3	1.50 (4)
Cs2—O22	3.25 (2)	O24—Li3	2.29 (4)
S1—O12	1.461 (15)	Li2—Li4	2.35 (4)
O24—Cs1—O21	105.5 (4)	O13—O12—Cs2	63.9 (7)
Li3—Cs1—O21	116.4 (6)	Cs1—O12—Cs2	59.5 (3)
O21—Cs1—O22	136.9 (4)	S1—O13—Cs2	98.8 (5)
O24—Cs1—O12	150.4 (6)	O12—O13—Cs2	88.6 (8)
Li3—Cs1—O12	112.9 (8)	S2—O21—Cs1	102.1 (3)
O21—Cs1—O12	101.5 (4)	O24—O22—Li2	155.3 (13)
O22—Cs1—O12	121.0 (5)	Li2—O22—Li3	118.5 (15)
Li4—Cs2—Li2	102.9 (19)	O24—O22—Cs2	130.7 (8)
Li4—Cs2—O11	63.6 (6)	Li3—O22—Cs2	85.5 (11)
Li2—Cs2—O11	112.6 (4)	O24—O22—Cs1	69.6 (6)
Li4—Cs2—O13	66.8 (16)	Li2—O22—Cs1	89.9 (9)
Li2—Cs2—O13	157.1 (6)	O24—O23—Li3	108.1 (18)
Li4—Cs2—O22	137.4 (17)	O23—O24—O22	98.5 (15)
O11—Cs2—O22	113.9 (4)	O22—O24—Li3	69.6 (11)
O13—Cs2—O22	144.0 (5)	O23—O24—Cs1	98.0 (7)
O12—S1—O11	113.2 (5)	O22—O24—Cs1	78.8 (8)
O11—S1—O13	101.8 (4)	Li3—O24—Cs1	68.1 (9)
O12—S1—Cs2	70.8 (6)	Cs2—Li2—O22	108.4 (12)
O13—S1—Cs1	96.2 (6)	O22—Li2—Li4	128.9 (15)
S1—O11—Cs2	105.0 (3)	Li4—Li2—Cs1	75.6 (8)
S1—O11—Cs1	93.8 (4)	O23—Li3—O22	71.5 (17)
S1—O12—O13	58.9 (9)	O23—Li3—Cs1	94.8 (6)
S1—O12—Cs1	104.8 (5)	O24—Li3—Cs1	69.0 (5)
O13—O12—Cs1	122.1 (7)	O22—Li3—Cs1	72.3 (8)
S1—O12—Cs2	85.8 (7)	Li2—Li4—Cs1	69.5 (9)

(II) caesium lithium rubidium sulfate

Crystal data

Cs0.90Li2.88Rb0.22(SO4)2	F(000) = 325
Mr = 350.53	Dx = 2.772 Mg m^−3
Monoclinic, Pc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P -2yc	Cell parameters from 8702 reflections
a = 5.0530 (2) Å	θ = 1.0–27.5°
b = 5.1990 (4) Å	µ = 5.75 mm^−1
c = 15.9840 (8) Å	T = 293 K
β = 90.297 (3)°	Prism, colorless
V = 419.90 (4) Å^3	0.09 × 0.08 × 0.06 mm
Z = 2

Data collection

KappaCCD diffractometer	1833 independent reflections
Radiation source: fine-focus sealed tube	1810 reflections with I > 2σ(I)
Horizonally mounted graphite crystal monochromator	Rint = 0.046
Detector resolution: 9 pixels mm^-1	θmax = 27.5°, θmin = 2.6°
ϕ scans and ω scans winth κ offsets	h = −6→6
Absorption correction: multi-scan multi-scan from symmetry-related measurements SORTAV (Blessing, 1995)	k = −6→6
Tmin = 0.632, Tmax = 0.750	l = −20→20
12898 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0519P)^2 + 0.1683P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.025	(Δ/σ)max < 0.001
wR(F^2) = 0.083	Δρmax = 1.07 e Å^−3
S = 1.22	Δρmin = −0.53 e Å^−3
1833 reflections	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
131 parameters	Extinction coefficient: 0.038 (3)
2 restraints	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.05 (2)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cs	−0.92955 (8)	0.73641 (5)	0.43372 (4)	0.02641 (15)	0.90
Rb	−0.4254 (9)	0.7880 (7)	0.5725 (3)	0.0592 (10)	0.22
S1	−0.9224 (3)	0.6654 (2)	0.14039 (9)	0.0165 (2)
S2	−0.4230 (2)	0.26658 (18)	0.34727 (8)	0.0150 (3)
O11	−0.9573 (7)	0.3843 (6)	0.1509 (2)	0.0270 (7)
O12	−0.6352 (8)	0.7213 (6)	0.1402 (3)	0.0227 (8)
O13	−1.0442 (10)	0.7448 (5)	0.0621 (3)	0.0230 (9)
O14	−1.0432 (8)	0.8017 (7)	0.2113 (2)	0.0225 (7)
O21	−0.5625 (6)	0.1038 (6)	0.2851 (2)	0.0261 (6)
O22	−0.4782 (7)	0.5377 (6)	0.3292 (2)	0.0300 (7)
O23	−0.1375 (9)	0.2181 (7)	0.3416 (3)	0.0265 (8)
O24	−0.5178 (9)	0.2059 (8)	0.4312 (3)	0.0280 (8)
Li1	−0.4158 (16)	0.1581 (18)	0.5448 (5)	0.0200 (11)	0.92
Li2	−0.9212 (14)	1.1540 (15)	0.2464 (4)	0.0200 (11)	0.96
Li3	−1.418 (2)	0.7820 (16)	0.2419 (6)	0.0213 (19)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cs	0.0261 (2)	0.0252 (2)	0.0280 (2)	−0.00027 (16)	0.00142 (12)	0.00056 (15)
Rb	0.056 (2)	0.0536 (19)	0.068 (3)	−0.0005 (15)	0.000 (2)	0.0065 (17)
S1	0.0157 (4)	0.0152 (5)	0.0185 (4)	0.0001 (4)	0.0000 (3)	−0.0008 (4)
S2	0.0156 (6)	0.0154 (5)	0.0138 (5)	0.0006 (3)	0.0003 (4)	−0.0004 (3)
O11	0.0370 (18)	0.0171 (16)	0.0267 (15)	−0.0031 (14)	−0.0023 (12)	−0.0016 (12)
O12	0.0145 (18)	0.0337 (18)	0.0199 (17)	−0.0007 (12)	−0.0008 (14)	−0.0008 (12)
O13	0.022 (2)	0.027 (2)	0.0196 (19)	0.0024 (10)	−0.0027 (16)	0.0044 (9)
O14	0.0178 (16)	0.0241 (15)	0.0257 (17)	−0.0016 (14)	0.0032 (13)	−0.0076 (14)
O21	0.0240 (15)	0.0243 (16)	0.0300 (14)	0.0054 (13)	−0.0058 (11)	−0.0094 (13)
O22	0.0372 (18)	0.0184 (15)	0.0346 (16)	0.0047 (13)	0.0067 (13)	0.0027 (13)
O23	0.0168 (17)	0.0368 (19)	0.0259 (18)	0.0028 (13)	−0.0039 (14)	−0.0055 (14)
O24	0.0247 (19)	0.0419 (19)	0.0174 (18)	−0.0035 (15)	0.0027 (15)	0.0049 (14)
Li1	0.018 (3)	0.016 (3)	0.026 (3)	0.000 (2)	0.000 (2)	0.001 (2)
Li2	0.018 (3)	0.016 (3)	0.026 (3)	0.000 (2)	0.000 (2)	0.001 (2)
Li3	0.029 (5)	0.025 (4)	0.010 (4)	−0.004 (3)	0.001 (3)	−0.001 (3)

Geometric parameters (Å, º)

Cs—Rb^i	3.365 (5)	O21—Rb^v	3.517 (6)
Cs—Rb	3.380 (5)	O21—Cs^viii	3.575 (4)
Rb—Li1^ii	1.975 (10)	O22—Cs^iii	3.391 (4)
Rb—Cs^iii	3.365 (5)	O23—Cs^ix	3.086 (4)
S1—O13	1.452 (5)	O23—Cs^iii	3.243 (4)
S1—O14	1.472 (4)	O24—Li1	1.900 (9)
S1—O12	1.480 (4)	O24—Rb^viii	3.166 (6)
S1—O11	1.482 (3)	O24—Cs^viii	3.208 (4)
S2—O24	1.462 (4)	Li1—Rb^viii	1.975 (10)
S2—O22	1.466 (3)	Li2—O23^x	1.908 (9)
S2—O23	1.468 (5)	Li2—O21^ii	1.930 (8)
S2—O21	1.481 (3)	Li2—O11^ii	1.948 (8)
O11—Rb^iv	2.818 (6)	Li2—S2^ii	3.039 (7)
O11—Rb^v	3.104 (6)	Li2—Rb^vi	3.764 (9)
O11—Cs^v	3.532 (3)	Li2—Rb^vii	3.774 (9)
O12—Rb^vi	2.969 (5)	Li2—Cs^ii	4.258 (8)
O12—Rb^v	3.053 (5)	Li3—O22^i	1.912 (9)
O13—Rb^vii	3.105 (5)	Li3—O21^x	1.953 (10)
O13—Cs^v	3.289 (4)	Li3—O12^i	1.982 (11)
O13—Rb^iv	3.379 (5)	Li3—S2^x	3.031 (9)
O13—Cs^vi	3.440 (3)	Li3—Rb^vii	3.512 (11)
O14—Li3	1.962 (12)	Li3—Rb^iv	4.015 (10)
O14—Li2	2.012 (9)	Li3—Cs^i	4.027 (10)
O14—Rb^vii	3.627 (6)
O22—Cs—O23^x	105.67 (11)	Li3^iii—O12—Rb^v	103.7 (3)
O22—Cs—O24^ii	76.20 (10)	Li1^v—O12—Rb^v	78.8 (3)
O23^x—Cs—O24^ii	66.16 (11)	Rb^vi—O12—Rb^v	119.4 (2)
O22—Cs—O23^i	73.02 (11)	S1—O13—Li1^iv	126.6 (4)
O23^x—Cs—O23^i	110.44 (14)	S1—O13—Rb^vii	115.9 (2)
O24^ii—Cs—O23^i	146.66 (12)	S1—O13—Cs^v	104.27 (16)
O22—Cs—O13^xi	102.79 (10)	Li1^iv—O13—Cs^v	106.2 (3)
O23^x—Cs—O13^xi	148.66 (13)	Rb^vii—O13—Cs^v	137.72 (18)
O24^ii—Cs—O13^xi	134.66 (11)	S1—O13—Rb^iv	87.94 (17)
O23^i—Cs—O13^xi	66.00 (10)	Li1^iv—O13—Rb^iv	70.9 (3)
O22—Cs—Rb^i	163.73 (9)	Rb^vii—O13—Rb^iv	106.55 (19)
O23^x—Cs—Rb^i	89.82 (12)	Cs^v—O13—Rb^iv	60.62 (10)
O24^ii—Cs—Rb^i	115.63 (10)	S1—O13—Cs^vi	131.7 (2)
O23^i—Cs—Rb^i	97.17 (12)	Li1^iv—O13—Cs^vi	83.0 (3)
O13^xi—Cs—Rb^i	61.01 (10)	Rb^vii—O13—Cs^vi	61.64 (10)
O22—Cs—Rb	79.71 (11)	Cs^v—O13—Cs^vi	101.16 (12)
O23^x—Cs—Rb	120.14 (10)	Rb^iv—O13—Cs^vi	140.36 (17)
O24^ii—Cs—Rb	57.38 (10)	S1—O14—Li3	124.9 (4)
O23^i—Cs—Rb	127.24 (10)	S1—O14—Li2	121.7 (3)
O13^xi—Cs—Rb	77.63 (11)	Li3—O14—Li2	105.8 (3)
Rb^i—Cs—Rb	97.03 (14)	S1—O14—Cs	130.4 (2)
O22—Cs—O22^i	103.95 (10)	Li3—O14—Cs	84.2 (3)
O23^x—Cs—O22^i	74.74 (10)	Li2—O14—Cs	76.4 (2)
O24^ii—Cs—O22^i	138.98 (10)	S1—O14—Rb^vii	91.93 (19)
O23^i—Cs—O22^i	42.35 (10)	Li3—O14—Rb^vii	70.8 (3)
O13^xi—Cs—O22^i	85.96 (10)	Li2—O14—Rb^vii	78.3 (3)
Rb^i—Cs—O22^i	74.90 (11)	Cs—O14—Rb^vii	137.58 (14)
Rb—Cs—O22^i	163.58 (9)	S2—O21—Li2^viii	125.5 (3)
O22—Cs—O13^xii	136.81 (10)	S2—O21—Li3^ix	123.3 (4)
O23^x—Cs—O13^xii	65.81 (10)	Li2^viii—O21—Li3^ix	110.8 (4)
O24^ii—Cs—O13^xii	61.44 (11)	S2—O21—Rb^v	117.51 (19)
O23^i—Cs—O13^xii	150.13 (12)	Li2^viii—O21—Rb^v	81.9 (2)
O13^xi—Cs—O13^xii	101.16 (12)	Li3^ix—O21—Rb^v	73.7 (3)
Rb^i—Cs—O13^xii	54.28 (10)	S2—O21—Cs^viii	96.07 (16)
Rb—Cs—O13^xii	71.04 (11)	Li2^viii—O21—Cs^viii	78.2 (2)
O22^i—Cs—O13^xii	113.14 (10)	Li3^ix—O21—Cs^viii	88.4 (3)
O22—Cs—O24	42.55 (9)	Rb^v—O21—Cs^viii	146.42 (12)
O23^x—Cs—O24	147.75 (11)	S2—O22—Li3^iii	138.8 (4)
O24^ii—Cs—O24	102.51 (12)	S2—O22—Cs	111.33 (18)
O23^i—Cs—O24	61.65 (10)	Li3^iii—O22—Cs	107.5 (3)
O13^xi—Cs—O24	60.53 (10)	S2—O22—Cs^iii	92.36 (17)
Rb^i—Cs—O24	121.44 (9)	Li3^iii—O22—Cs^iii	91.4 (3)
Rb—Cs—O24	67.61 (10)	Cs—O22—Cs^iii	103.95 (10)
O22^i—Cs—O24	104.01 (10)	S2—O23—Li2^ix	130.3 (4)
O13^xii—Cs—O24	137.40 (10)	S2—O23—Cs^ix	116.3 (2)
O22—Cs—O11^xi	121.18 (9)	Li2^ix—O23—Cs^ix	92.5 (3)
O23^x—Cs—O11^xi	126.72 (10)	S2—O23—Cs^iii	98.38 (18)
O24^ii—Cs—O11^xi	100.16 (9)	Li2^ix—O23—Cs^iii	108.8 (3)
O23^i—Cs—O11^xi	106.50 (10)	Cs^ix—O23—Cs^iii	110.44 (14)
O13^xi—Cs—O11^xi	40.84 (8)	S2—O24—Li1	144.7 (4)
Rb^i—Cs—O11^xi	48.15 (10)	S2—O24—Rb^viii	139.0 (3)
Rb—Cs—O11^xi	53.32 (10)	S2—O24—Cs^viii	113.0 (2)
O22^i—Cs—O11^xi	113.19 (9)	Li1—O24—Cs^viii	93.5 (3)
O13^xii—Cs—O11^xi	62.96 (9)	Rb^viii—O24—Cs^viii	64.04 (12)
O24—Cs—O11^xi	84.05 (8)	S2—O24—Cs	92.21 (19)
O22—Cs—O21^ii	54.44 (8)	Li1—O24—Cs	104.7 (3)
O23^x—Cs—O21^ii	54.97 (10)	Rb^viii—O24—Cs	128.77 (16)
O24^ii—Cs—O21^ii	41.10 (9)	Cs^viii—O24—Cs	102.51 (12)
O23^i—Cs—O21^ii	108.08 (10)	O24—Li1—O13^xiii	110.8 (4)
O13^xi—Cs—O21^ii	156.17 (9)	O24—Li1—Rb^viii	109.5 (5)
Rb^i—Cs—O21^ii	141.81 (8)	O13^xiii—Li1—Rb^viii	104.1 (4)
Rb—Cs—O21^ii	90.10 (10)	O24—Li1—O12^xi	122.7 (5)
O22^i—Cs—O21^ii	105.12 (8)	O13^xiii—Li1—O12^xi	110.3 (4)
O13^xii—Cs—O21^ii	93.84 (9)	Rb^viii—Li1—O12^xi	96.9 (4)
O24—Cs—O21^ii	95.99 (8)	O24—Li1—Li3^xiii	159.2 (4)
O11^xi—Cs—O21^ii	140.51 (8)	O13^xiii—Li1—Li3^xiii	81.0 (4)
Li1^ii—Rb—O11^xiii	112.8 (3)	Rb^viii—Li1—Li3^xiii	82.7 (3)
Li1^ii—Rb—O12^xii	41.7 (3)	O12^xi—Li1—Li3^xiii	37.1 (3)
O11^xiii—Rb—O12^xii	114.30 (19)	O24—Li1—Rb	89.7 (4)
Li1^ii—Rb—O12^xi	159.0 (3)	O13^xiii—Li1—Rb	75.0 (3)
O11^xiii—Rb—O12^xi	81.86 (15)	Rb^viii—Li1—Rb	159.2 (5)
O12^xii—Rb—O12^xi	119.4 (2)	O12^xi—Li1—Rb	65.0 (3)
Li1^ii—Rb—O11^xi	113.2 (3)	Li3^xiii—Li1—Rb	76.7 (3)
O11^xiii—Rb—O11^xi	117.1 (2)	O24—Li1—Cs^ix	78.4 (3)
O12^xii—Rb—O11^xi	77.84 (15)	O13^xiii—Li1—Cs^ix	65.7 (2)
O12^xi—Rb—O11^xi	45.84 (12)	Rb^viii—Li1—Cs^ix	63.5 (3)
Li1^ii—Rb—O13^xiv	37.8 (3)	O12^xi—Li1—Cs^ix	156.4 (4)
O11^xiii—Rb—O13^xiv	75.71 (15)	Li3^xiii—Li1—Cs^ix	122.3 (3)
O12^xii—Rb—O13^xiv	64.54 (13)	Rb—Li1—Cs^ix	130.8 (3)
O12^xi—Rb—O13^xiv	156.1 (2)	O24—Li1—Cs^viii	56.8 (3)
O11^xi—Rb—O13^xiv	141.83 (18)	O13^xiii—Li1—Cs^viii	149.2 (4)
Li1^ii—Rb—O24^ii	34.5 (3)	Rb^viii—Li1—Cs^viii	61.9 (3)
O11^xiii—Rb—O24^ii	130.99 (19)	O12^xi—Li1—Cs^viii	99.0 (3)
O12^xii—Rb—O24^ii	67.58 (14)	Li3^xiii—Li1—Cs^viii	120.8 (3)
O12^xi—Rb—O24^ii	142.9 (2)	Rb—Li1—Cs^viii	128.3 (3)
O11^xi—Rb—O24^ii	111.19 (18)	Cs^ix—Li1—Cs^viii	83.68 (17)
O13^xiv—Rb—O24^ii	60.94 (14)	O24—Li1—Cs^iii	70.4 (3)
Li1^ii—Rb—Li1	159.2 (5)	O13^xiii—Li1—Cs^iii	47.6 (2)
O11^xiii—Rb—Li1	74.42 (18)	Rb^viii—Li1—Cs^iii	142.5 (4)
O12^xii—Rb—Li1	154.9 (2)	O12^xi—Li1—Cs^iii	114.8 (3)
O12^xi—Rb—Li1	36.22 (17)	Li3^xiii—Li1—Cs^iii	110.4 (3)
O11^xi—Rb—Li1	77.37 (18)	Rb—Li1—Cs^iii	50.77 (16)
O13^xiv—Rb—Li1	139.3 (2)	Cs^ix—Li1—Cs^iii	80.51 (15)
O24^ii—Rb—Li1	125.9 (2)	Cs^viii—Li1—Cs^iii	126.9 (2)
Li1^ii—Rb—Cs^iii	84.9 (3)	O24—Li1—Cs	50.3 (2)
O11^xiii—Rb—Cs^iii	69.01 (12)	O13^xiii—Li1—Cs	116.6 (4)
O12^xii—Rb—Cs^iii	125.25 (15)	Rb^viii—Li1—Cs	138.6 (4)
O12^xi—Rb—Cs^iii	115.17 (15)	O12^xi—Li1—Cs	76.2 (3)
O11^xi—Rb—Cs^iii	153.17 (16)	Li3^xiii—Li1—Cs	109.5 (3)
O13^xiv—Rb—Cs^iii	64.08 (12)	Rb—Li1—Cs	50.20 (15)
O24^ii—Rb—Cs^iii	72.08 (13)	Cs^ix—Li1—Cs	127.1 (2)
Li1—Rb—Cs^iii	79.70 (17)	Cs^viii—Li1—Cs	78.72 (14)
Li1^ii—Rb—O13^xiii	140.6 (3)	Cs^iii—Li1—Cs	71.77 (14)
O11^xiii—Rb—O13^xiii	44.25 (11)	O23^x—Li2—O21^ii	108.0 (4)
O12^xii—Rb—O13^xiii	158.0 (2)	O23^x—Li2—O11^ii	117.8 (4)
O12^xi—Rb—O13^xiii	60.34 (12)	O21^ii—Li2—O11^ii	114.7 (4)
O11^xi—Rb—O13^xiii	106.15 (14)	O23^x—Li2—O14	101.9 (4)
O13^xiv—Rb—O13^xiii	106.55 (19)	O21^ii—Li2—O14	104.6 (4)
O24^ii—Rb—O13^xiii	127.6 (2)	O11^ii—Li2—O14	108.3 (4)
Li1—Rb—O13^xiii	34.12 (16)	O23^x—Li2—S2^ii	91.1 (3)
Cs^iii—Rb—O13^xiii	58.37 (11)	O21^ii—Li2—S2^ii	23.38 (14)
Li1^ii—Rb—Cs	87.1 (3)	O11^ii—Li2—S2^ii	111.8 (3)
O11^xiii—Rb—Cs	153.50 (17)	O14—Li2—S2^ii	125.1 (3)
O12^xii—Rb—Cs	92.19 (14)	O23^x—Li2—Li3	70.6 (3)
O12^xi—Rb—Cs	84.36 (14)	O21^ii—Li2—Li3	131.9 (4)
O11^xi—Rb—Cs	65.85 (11)	O11^ii—Li2—Li3	106.6 (3)
O13^xiv—Rb—Cs	119.52 (16)	O14—Li2—Li3	36.5 (2)
O24^ii—Rb—Cs	58.58 (12)	S2^ii—Li2—Li3	141.6 (3)
Li1—Rb—Cs	81.09 (17)	O23^x—Li2—Li3^iii	125.7 (4)
Cs^iii—Rb—Cs	97.03 (14)	O21^ii—Li2—Li3^iii	34.8 (2)
O13^xiii—Rb—Cs	109.30 (15)	O11^ii—Li2—Li3^iii	115.2 (3)
Li1^ii—Rb—Li3^xiv	63.4 (3)	O14—Li2—Li3^iii	71.6 (3)
O11^xiii—Rb—Li3^xiv	81.6 (2)	S2^ii—Li2—Li3^iii	58.1 (2)
O12^xii—Rb—Li3^xiv	34.33 (18)	Li3—Li2—Li3^iii	105.1 (3)
O12^xi—Rb—Li3^xiv	106.3 (2)	O23^x—Li2—Cs	56.5 (2)
O11^xi—Rb—Li3^xiv	83.0 (2)	O21^ii—Li2—Cs	71.1 (2)
O13^xiv—Rb—Li3^xiv	62.6 (2)	O11^ii—Li2—Cs	173.6 (3)
O24^ii—Rb—Li3^xiv	96.54 (19)	O14—Li2—Cs	71.7 (2)
Li1—Rb—Li3^xiv	137.2 (3)	S2^ii—Li2—Cs	72.34 (15)
Cs^iii—Rb—Li3^xiv	123.7 (2)	Li3—Li2—Cs	69.4 (2)
O13^xiii—Rb—Li3^xiv	123.8 (2)	Li3^iii—Li2—Cs	71.1 (2)
Cs—Rb—Li3^xiv	124.2 (2)	O23^x—Li2—Rb^vi	164.1 (4)
O13—S1—O14	110.6 (2)	O21^ii—Li2—Rb^vi	67.6 (2)
O13—S1—O12	110.7 (3)	O11^ii—Li2—Rb^vi	55.4 (2)
O14—S1—O12	108.5 (2)	O14—Li2—Rb^vi	94.1 (3)
O13—S1—O11	109.15 (19)	S2^ii—Li2—Rb^vi	79.85 (18)
O14—S1—O11	109.7 (2)	Li3—Li2—Rb^vi	124.2 (3)
O12—S1—O11	108.13 (19)	Li3^iii—Li2—Rb^vi	59.9 (2)
O13—S1—Rb^v	102.6 (2)	Cs—Li2—Rb^vi	130.9 (2)
O14—S1—Rb^v	146.8 (2)	O23^x—Li2—Rb^vii	100.7 (3)
O12—S1—Rb^v	56.27 (15)	O21^ii—Li2—Rb^vii	151.2 (3)
O11—S1—Rb^v	58.28 (15)	O11^ii—Li2—Rb^vii	46.6 (2)
O13—S1—Rb^iv	68.50 (17)	O14—Li2—Rb^vii	70.3 (2)
O14—S1—Rb^iv	104.50 (17)	S2^ii—Li2—Rb^vii	158.4 (3)
O12—S1—Rb^iv	144.30 (17)	Li3—Li2—Rb^vii	60.0 (2)
O11—S1—Rb^iv	46.34 (15)	Li3^iii—Li2—Rb^vii	124.5 (3)
Rb^v—S1—Rb^iv	88.45 (9)	Cs—Li2—Rb^vii	129.3 (2)
O13—S1—Cs^v	54.63 (14)	Rb^vi—Li2—Rb^vii	84.19 (19)
O14—S1—Cs^v	154.96 (17)	O23^x—Li2—Cs^ii	46.1 (2)
O12—S1—Cs^v	96.18 (17)	O21^ii—Li2—Cs^ii	83.3 (2)
O11—S1—Cs^v	64.43 (12)	O11^ii—Li2—Cs^ii	96.5 (3)
Rb^v—S1—Cs^v	53.21 (9)	O14—Li2—Cs^ii	147.1 (3)
Rb^iv—S1—Cs^v	52.88 (9)	S2^ii—Li2—Cs^ii	60.10 (13)
O13—S1—Rb^vi	79.98 (19)	Li3—Li2—Cs^ii	116.0 (3)
O14—S1—Rb^vi	97.60 (17)	Li3^iii—Li2—Cs^ii	117.2 (3)
O11—S1—Rb^vi	144.82 (15)	Cs—Li2—Cs^ii	81.27 (14)
Rb^v—S1—Rb^vi	86.73 (11)	Rb^vi—Li2—Cs^ii	118.13 (19)
Rb^iv—S1—Rb^vi	146.19 (17)	Rb^vii—Li2—Cs^ii	116.88 (19)
Cs^v—S1—Rb^vi	98.94 (9)	O22^i—Li3—O21^x	104.5 (5)
O14—S1—Rb^vii	66.27 (18)	O22^i—Li3—O14	112.0 (5)
O12—S1—Rb^vii	119.10 (15)	O21^x—Li3—O14	114.0 (5)
O11—S1—Rb^vii	131.47 (15)	O22^i—Li3—O12^i	113.8 (5)
Rb^v—S1—Rb^vii	146.24 (17)	O21^x—Li3—O12^i	102.7 (5)
Rb^iv—S1—Rb^vii	86.36 (11)	O14—Li3—O12^i	109.5 (5)
Cs^v—S1—Rb^vii	98.55 (8)	O22^i—Li3—S2^x	98.3 (4)
Rb^vi—S1—Rb^vii	79.43 (8)	O21^x—Li3—S2^x	24.10 (17)
O24—S2—O22	109.0 (2)	O14—Li3—S2^x	96.1 (4)
O24—S2—O23	110.2 (3)	O12^i—Li3—S2^x	125.6 (4)
O22—S2—O23	109.8 (2)	O22^i—Li3—Li1^iv	142.4 (4)
O24—S2—O21	109.6 (2)	O21^x—Li3—Li1^iv	105.7 (4)
O22—S2—O21	109.1 (2)	O14—Li3—Li1^iv	74.8 (4)
O23—S2—O21	109.0 (2)	O12^i—Li3—Li1^iv	37.3 (3)
O24—S2—Li3^ix	109.5 (3)	S2^x—Li3—Li1^iv	118.1 (3)
O22—S2—Li3^ix	133.8 (2)	O22^i—Li3—Li2	121.2 (5)
O23—S2—Li3^ix	79.2 (3)	O21^x—Li3—Li2	76.5 (3)
O24—S2—Li2^viii	99.8 (2)	O14—Li3—Li2	37.6 (2)
O22—S2—Li2^viii	85.6 (2)	O12^i—Li3—Li2	123.4 (4)
O23—S2—Li2^viii	138.3 (2)	S2^x—Li3—Li2	59.3 (2)
Li3^ix—S2—Li2^viii	63.5 (3)	Li1^iv—Li3—Li2	87.4 (3)
O24—S2—Cs^iii	91.29 (19)	O22^i—Li3—Li2^i	104.9 (5)
O22—S2—Cs^iii	64.65 (16)	O21^x—Li3—Li2^i	34.4 (3)
O23—S2—Cs^iii	58.83 (15)	O14—Li3—Li2^i	138.0 (4)
O21—S2—Cs^iii	158.87 (15)	O12^i—Li3—Li2^i	71.2 (4)
Li3^ix—S2—Cs^iii	137.7 (2)	S2^x—Li3—Li2^i	58.4 (2)
Li2^viii—S2—Cs^iii	150.27 (15)	Li1^iv—Li3—Li2^i	88.3 (3)
O24—S2—Cs	65.20 (18)	Li2—Li3—Li2^i	105.1 (3)
O22—S2—Cs	47.64 (14)	O22^i—Li3—Rb^vii	169.9 (5)
O23—S2—Cs	142.76 (16)	O21^x—Li3—Rb^vii	74.0 (3)
O21—S2—Cs	106.98 (14)	O14—Li3—Rb^vii	77.3 (3)
Li3^ix—S2—Cs	138.0 (2)	O12^i—Li3—Rb^vii	57.7 (3)
Li2^viii—S2—Cs	76.06 (14)	S2^x—Li3—Rb^vii	84.2 (2)
Cs^iii—S2—Cs	83.98 (2)	Li1^iv—Li3—Rb^vii	33.9 (2)
O24—S2—Cs^ix	74.82 (18)	Li2—Li3—Rb^vii	68.5 (2)
O22—S2—Cs^ix	149.00 (16)	Li2^i—Li3—Rb^vii	68.1 (2)
O21—S2—Cs^ix	97.65 (13)	O22^i—Li3—Cs	59.5 (3)
Li3^ix—S2—Cs^ix	67.0 (2)	O21^x—Li3—Cs	90.6 (3)
Li2^viii—S2—Cs^ix	124.70 (15)	O14—Li3—Cs	66.1 (3)
Cs^iii—S2—Cs^ix	84.75 (3)	O12^i—Li3—Cs	166.5 (4)
Cs—S2—Cs^ix	138.06 (4)	S2^x—Li3—Cs	67.90 (19)
O24—S2—Cs^viii	47.38 (18)	Li1^iv—Li3—Cs	140.9 (4)
O22—S2—Cs^viii	127.42 (16)	Li2—Li3—Cs	61.6 (2)
O23—S2—Cs^viii	122.15 (16)	Li2^i—Li3—Cs	121.0 (3)
O21—S2—Cs^viii	62.39 (14)	Rb^vii—Li3—Cs	130.0 (3)
Li3^ix—S2—Cs^viii	68.11 (19)	O22^i—Li3—Rb^iv	90.0 (3)
Li2^viii—S2—Cs^viii	61.46 (14)	O21^x—Li3—Rb^iv	150.3 (5)
Cs^iii—S2—Cs^viii	138.15 (4)	O14—Li3—Rb^iv	82.9 (3)
Cs—S2—Cs^viii	83.36 (3)	O12^i—Li3—Rb^iv	47.6 (2)
Cs^ix—S2—Cs^viii	78.656 (18)	S2^x—Li3—Rb^iv	171.3 (3)
S1—O11—Li2^viii	133.2 (3)	Li1^iv—Li3—Rb^iv	53.2 (2)
S1—O11—Rb^iv	111.30 (18)	Li2—Li3—Rb^iv	118.0 (3)
Li2^viii—O11—Rb^iv	103.2 (3)	Li2^i—Li3—Rb^iv	117.2 (3)
S1—O11—Rb^v	97.76 (16)	Rb^vii—Li3—Rb^iv	87.1 (3)
Li2^viii—O11—Rb^v	93.5 (3)	Cs—Li3—Rb^iv	119.0 (3)
Rb^iv—O11—Rb^v	117.06 (19)	O22^i—Li3—Cs^i	45.6 (3)
S1—O11—Cs^v	93.34 (13)	O21^x—Li3—Cs^i	62.6 (3)
Li2^viii—O11—Cs^v	131.1 (3)	O14—Li3—Cs^i	144.8 (4)
Rb^iv—O11—Cs^v	62.84 (13)	O12^i—Li3—Cs^i	105.1 (4)
Rb^v—O11—Cs^v	60.83 (11)	S2^x—Li3—Cs^i	67.59 (19)
S1—O12—Li3^iii	124.6 (4)	Li1^iv—Li3—Cs^i	140.3 (4)
S1—O12—Li1^v	127.9 (4)	Li2—Li3—Cs^i	122.0 (3)
Li3^iii—O12—Li1^v	105.7 (4)	Li2^i—Li3—Cs^i	60.3 (2)
S1—O12—Rb^vi	121.4 (2)	Rb^vii—Li3—Cs^i	128.4 (3)
Li3^iii—O12—Rb^vi	88.0 (3)	Cs—Li3—Cs^i	78.80 (18)
S1—O12—Rb^v	99.95 (18)	Rb^iv—Li3—Cs^i	117.8 (2)

Symmetry codes: (i) x−1, y, z; (ii) x, y+1, z; (iii) x+1, y, z; (iv) x−1, −y+1, z−1/2; (v) x, −y+1, z−1/2; (vi) x, −y+2, z−1/2; (vii) x−1, −y+2, z−1/2; (viii) x, y−1, z; (ix) x+1, y−1, z; (x) x−1, y+1, z; (xi) x, −y+1, z+1/2; (xii) x, −y+2, z+1/2; (xiii) x+1, −y+1, z+1/2; (xiv) x+1, −y+2, z+1/2.